JPH06510801A - Catalyst system for the production of amide transition metal compounds and isotactic polypropylene - Google Patents

Abstract

Certain bridged and unbridged amido transition metal compounds of the Group IV-B metals are disclosed. These compounds may be used in a catalyst system comprising the amido transition metal compound and an alumoxane. Also disclosed is a process using the catalyst system for the production of high molecular weight polyolefins and, particularly, high molecular weight isotactic polypropylene.

Description

[Detailed description of the invention] Catalyst system for the production of amide transition metal compounds and isotactic polypropylene The present invention provides certain bridged amide transition metal compounds and uncrosslinked amide transition metal compounds of Group 1 VB metals. a catalyst system comprising a de-transition metal compound, an amide-transition metal compound and an alumoxane; This catalyst system can also be used to develop high molecular weight polyolefins, especially high molecular weight isotactic compounds. Various compounds obtained through the polymerization of α-olefins are used to produce polypropylene. Objects exhibit significant differences in their chemical and physical properties. These differences are due to differences in molecular structure. However, it reflects the use of certain monomers or combinations of monomers. It may be due essentially to the use of It may also be caused by Polymers of α-olefins having 3 or more carbon atoms are As an attribute, side chain hydrocarbon groups are bonded to the polymer main chain. However, these carbonization The stereochemical arrangement of hydrogen groups is determined by the interaction of monomers, catalysts, and coordination polymers during polymerization. It is a product of Any side chain hydrocarbon group can be idealized into an extended configuration. located on either side of the plane defined by the carbon atoms of the polymer backbone. It is thought that then.

As previously pointed out, a given olefin polymer of a given molecular weight The physical properties of are due to the arrangement of these side chain hydrocarbon groups along the polymer backbone. greatly influenced by. Sturdy polymers tend to have stereochemical regularity and adjacent hydrocarbon groups are on the same side of the polymer backbone, or This means that they are reversed at very regular intervals. These arrangements also promotes crystallization, thereby adding stiffness and strength to the crystallized polymer.

Other critical factors that influence the properties of polymers are the monomers and comonomers. Type and relative concentration of polymer, weight average molecular weight (My) of polymer molecules from the whole resin, These are the molecular weight distribution (MID) and the composition distribution of the resin. Requires high strength and low creep For the desired end use, the Mw of the resin must generally be 100,000 or higher. No.

Atactic, normal isotactic, isotactic stereo blocks There are five types of stereoregularity: syndiotactic and hemiisotactic. Kuchishi.

(also called Qi) has been revealed. These stereoregular arrangements were first demonstrated All of the above are for polypropylene, but theoretically, the number of carbon atoms is Regarding polymers consisting of 3 or more olefins, cyclic olefins or internal olefins Similarly, each stereoregular configuration may be adopted.

Atactic polyolefins are mainly composed of side chain hydrocarbon groups bonded to the main chain of the polymer molecule. It is a polyolefin that is thought to have no spatial regularity in its chains. . This random structure is caused by polymerization in which methylene carbons and methine carbons are arranged alternately. It is represented as having methine carbon side chain substituents randomly oriented on the body main chain. Mail The chin carbon has a random configuration of R and S, and adjacent pairs of the same configuration ( ``meso'' or ``m'' diat) or adjacent pairs of different configurations (``racemic'' or r rJ diat). Atactic type polymer is meso type diat and racemic diatoids in approximately equal proportions. Atactic polyolefin is It shows no regularity, and there is no regularity in the configuration of the repeating units in the polymer chain. Since they cannot be seen, they are amorphous substances. Atactic polyolefin is , because the resin exhibits little, if any, degree of crystallinity, Regardless of average molecular weight, it is generally unsuitable for applications that require high strength.

Isotactic polyolefins have side chain hydrocarbon groups that lie in the plane of the polymer main chain. In contrast, these polyolefins are arranged in spaces on the same side. Isotakuchi For example, in block polypropylene, an isotactic structure typically refers to The side chain methyl group bonded to the 3-position carbon atom of the subsequent monomer unit forms the carbon skeleton of the polymer. It can be described as being on the same side of an imaginary plane passing through the chain. For example, as below , the methyl groups are all on either side of the plane, above or below.

Ru. Bovey's NMR notation for isotactic pentads is [,,,m mm, , ]. Here, each ``field'' is a ``meso'' diato, in other words, Represents a series of methyl groups on the same side of the plane.

In the normal isotactic structure of polyolefin, Except for random errors, all monomeric units have the same stereochemical configuration. mosquito Such random errors almost always appear as isolated configuration inversions, and the immediately next α - When the olefin monomer is inserted, the original R or S is corrected in the growing polymer chain. Three-dimensional arrangement is restored.

The formation reaction of stereoblock isotactic polymers involves the growth site being in a chain. The formation of a normal isotactic structure in the way it reacts with stereochemical errors. It is different from the formation reaction. As mentioned above, normal isotactic chains are Moderators, i.e., ensure that the catalytically active metal species and its surrounding ligands remain in the same position throughout monomer insertion. It continues to direct body chemical selection, so it reverts to its original configuration after a mistake.

In stereoblock growth, the catalytically active metal site itself has an R configuration. From one that instructs the insertion of a monomer of the S configuration to one that instructs the insertion of a monomer with the S configuration Change into something. The shape of the isotactic stereo block is as shown below. be.

A catalyst system has been discovered that produces isotactic stereoblock polyolefins. It has been pointed out that a bending microstructure may exist long before the The generation mechanism is based on the conventional Ziegler-Natsuta mechanism, as described by Langer, A. W, Lect, Bienn, Polym, Symp, 7th ( 1974); Ann, N.Y., Acad, Sci., 295. 110 ~126 (1977). This kind of polypropylene and its The first reported example of a catalyst for producing it in pure form was U.S. Pat. No. 4.522. ．． In No. 982.

The length of each block with the same configuration in the stereoblock structure depends on the reaction conditions. It changes significantly by changing the conditions. Only the error part in the chain is the resin product In general, normal isotactic polymers and , isotactics with long block length (more than 50 isotactic configurations) Teleoblock polymers have similar properties.

Polyolefins with high isotacticity exhibit a high degree of crystallinity. Therefore, eye If the weight average molecular weight of the sotactic polyolefin exceeds about 100,000, Also well suited for end uses requiring high strength.

Syndiotactic polyolefins are bonded to the main chain of the polymer molecule, as shown below. The combined side chain hydrocarbon groups intersect one after another from one side of the plane of the polymer main chain to the other. It is a polyolefin that replaces

In NMR notation, this segment (i.e., pentad) is [,,,rrr, , ]. where each rrJ is a "racemic" diatotype, in other words: It represents a series of methyl groups arranged in alternating directions in opposite directions to the plane. r in chain The proportion of diatoms determines the syndiotactic degree of the polymer. Shinjio Highly tactical polymers are generally highly crystalline and often have a high isotactic property. It exhibits a high melting point similar to the tick polymorph. Same as isotactic polyolefin Similarly, syndiotactic polyolefins can exhibit high crystallinity.

Therefore, if the MW exceeds about 100,000, it is suitable for applications that require high strength. Ru.

For any of the aforementioned materials, the properties of the final resin and suitability for the particular application will vary. The properties are determined by the type of tacticity, melting point, average molecular weight, molecular weight distribution, and monomer of the substance. The type and content of comonomers and comonomers, their order distribution, and the functionality of the tip or terminal group. Depends on nothing. Therefore, in order to produce such stereoregular polyolefins, The catalyst system for One must be flexible regarding the choice of comonomers. Furthermore, the catalyst The system combines such polymers with top functional groups such as olefinic unsaturation and/or terminal functional groups. It must be possible to produce it with or without functional groups.

Moreover, such catalysts require sufficient production rates as a constraint for commercial implementation. It must be possible to produce such a resin. Most preferably the catalyst system Post-processing to remove residual catalyst to an extent acceptable for the desired end use. Such that a resin product requiring no processing is obtained at that productivity rate. be. Finally, an important aspect of industrial catalyst systems is their ability to withstand various processes and conditions. It is adaptability.

Conventional titanium-based Ziegler-Natsuta catalysts for the production of isotactic polymers are It is well known to business operators. These industrial catalysts are suitable for producing highly crystalline, high molecular weight materials. Suitable enough. However, these catalyst systems have limited molecular weight, molecular weight distribution, and There are limits to the control of Shichi.

These conventional catalysts contain several types of active sites, so the composition can be changed during copolymerization. Its ability to control distribution becomes more limited.

(1984) and Kaminsky, ? , others, ^ngew, Chew, Int, Ed.

Eng., 24.507-508 (1985), using alumoxane as a cocatalyst. A new method for producing isotactic polymers using metallocenes as activators It was reported that this metallocene normally exhibits chirality in the transition metal of the metallocene. center.

Catalysts that produce isotactic polyolefins are disclosed in U.S. Patent No. 4.794.096. It is also disclosed in the issue. This patent includes a chimney activated with an alumoxane cocatalyst. A typical stereorigid metallocene is disclosed, and this The medium has been reported to polymerize olefins as isotactic polyolefins. ing. Alumoxane-coated methane, which has been reported to undergo stereoregular polymerization, The structure of locene is ethylene-bridged bis-indenyl- and bis-tetra hydroindenyl-titanium and zirconium OV) catalyst. Such a catalyst First, the system is fi ld et al.

J, Organomet, Chem, 232.233-247 (198 2), and was subsequently synthesized and studied by Even and Kaminsky mentioned above. Other papers have reported stereoregular polymerization of α-olefins. Furthermore, the west German Patent Application No. 3443087 (1986) describes such a stereorigid metallothesis. The bridge length of the metallocene can be from 01 to C4 hydrocarbon, and the metallocene ring can be monocyclic. However, it has been reported that it may be bicyclic, but it must be asymmetric; No proof has been made. U.S. Patent No. 4.794.096 and West German Patent No. 4.794.096 mentioned above. In contrast to the metallocene catalyst disclosed in Application Publication No. 3,443,087, the present invention Some use achiral catalysts to produce highly isotactic polymers. can be built.

The use of transition metal-based catalysts, in which an amide group is bonded to the transition metal, is an effective method for polymer polishing. It has attracted a certain amount of attention in the research field. Tris-amide zirconium catalyst U.S. Patent No. 4.77 discloses a method for producing syndiotactic polystyrene using No. 4.301. In this specification, zirconium compounds are Its combination with xane as a polymerization catalyst is taught. Shinjiotakutchi Polymers are vinylaceous polymers commonly known to produce syndiotactic polymers. Polymerization of aromatic monomers using tris-amide zirconium/alumoxane catalyst You get it when you do.

European Patent No. 349.886 describes titanium bonded with saturated alkyl-substituted amide groups. is reported to provide an active catalyst in the presence of alumoxane. This catalyst system is It produces a polyethylene copolymer with a highly random structure and narrow molecular weight distribution.

European Patent No. 349.886 discloses the prior art amide containing No. The rVB group metal catalyst is also mentioned, and when this catalyst is applied to copolymerization, suffer from various disadvantages such as low molecular weight products, wide molecular weight distribution, and low catalytic activity. It is reported that.

It is desirable for stereoregular polymers in applications where other moldable plastics are not suitable. in terms of their high strength and other physical properties, as well as their usefulness in the production of stereoregular polymers. As disclosed herein, there are currently only a few methods available. The requirements for catalysts for producing high molecular weight, high isotactic polymers are There is a necessity. What is also desirable is that it can be easily molded and molded to suit its end use. and/or machinable polymers for contaminant (residual catalyst) removal. Such catalysts must have high activity so that they can be produced without treatment. Ru. It would also be desirable to produce catalysts useful in the production of ethylene-based polymers.

Summary of the invention The present invention provides a catalyst system for producing highly crystalline polyolefins using alumoxane as a promoter. The bridge whose transition metal component is represented by the general formula below is an amide transition metal compound. A catalyst system is disclosed.

In the above formula, the symbol is zirconium, hafnium or titanium, and N is three substituents. , y is 1 or 0, and the bridge between the nitrogen atoms is a group 2 is 2-V, and X and X' are monovalent anions. ionizable ligands, such as halides, hydrides, substituted or unsubstituted C1-C3 hydrocarbons. element, alkoxide, aryloxide, amide, arylamide, phosphite, aryl phosphite, etc., or X and X' together are divalent residues, e.g. Reden, cyclometalization (cyclometal 1ated) Hydrocarbon or other divalent anionic compound is a rate ligand, etc., and T is an unsubstituted carbon containing a Group 1 VA or Group VIA element. The covalent bridge selected from the group consisting of hydrocarbons and hydrocarbons is a group in which R and R' is a hydrocarbon having 1 to 30 carbon atoms each independently having one branch; Hydrocarbons having 1 to 30 carbon atoms with several branches, halogen groups, amide groups, Suphyto group, silyl group, alkoxy group, alkylpolide group, 01-C30 carbonization Group 1 VA metalloid group substituted with hydrogen and substituted 01-C1° hydrocarbon group and one or more hydrogen atoms are halogen group, amide group, phosphite group, atom substituted by a leukoxy group or other group containing a Lewis acid or Lewis basic functional group. is a group selected from the group consisting of C5-C30 hydrocarbon groups.

Additionally, polymerization methods using the above catalyst systems are also disclosed. This catalyst system is an amide transition gold It is produced by combining alumoxane and alumoxane, but it is produced by solution polymerization method. , slurry polymerization, gas phase polymerization, or high pressure polymerization. The above mentioned The medium can also be produced in supported form. The catalyst system of the present invention is suitable for homopolymerization of ethylene and Tylene or propylene and α-olefin or cyclic olefin or di In addition to copolymerization with ene and other unsaturated monomers, propylene can be Polymerizes to isotactic polypropylene.

Description of preferred specific embodiments ^, Transition metal components The Group 1 VB transition metal component of this catalyst system is represented by the general formula below. has the following meaning.

Violet is zirconium, titanium or hafnium.

N is a nitrogen atom with three substituents.

y is 1 or 0, and each bridge between nitrogen atoms represents the presence or absence of a group. Yes, 2 is 2-y.

Each R independently has one branch and has 1 to 30 carbon atoms (preferably 3 ~30) hydrocarbons having multiple branches and having 1 to 30 (preferably 3) carbon atoms ~30) Hydrocarbons, halogen groups, amide groups, phosphite groups, silyl groups, alkyl xy group, alkylpolide group, substituted C1-C1° hydrocarbon group, and one or more The above hydrogen atoms are halogen group, amide group, phosphite group, alkoxy group or their C2 substituted by a group containing another Lewis acid or Lewis basic functional group ~C1° hydrocarbon group, group rVA metalloid substituted with C1-C9° hydrocarbon C0 to C5° selected from group rVA of the periodic table of metalloid elements A group selected from the group consisting of hydrocarbon-substituted metalloid groups.

Each X is independently a monovalent anionic ligand, such as a halide, hydride, substituted or unsubstituted C7-C20 hydrocarbons, alkoxides, aryloxides, amide do, arylamide, phosphite, arylphosphite, etc., or both X and X' Alkylidene, cyclometalated hydrocarbon or other divalent anion as a whole more specifically, X is a general 2N(R)2 ligand; (where R has the same meaning as explained above), most specifically It is a silylamide group of the general formula N[5i(R)]2.

T is a covalent bridge group containing a Group 1 VA or Group II element, for example, Examples include, but are not limited to, dialkyl silicon groups, alkylaryl silicon groups, Base group, diaryl silicon group, dialkyl germanium group, alkylaryl gel manium group, diaryl germanium group, alkyl phosphine, arylphosphine amine, alkylamine group, arylamine group, oxygen group or sulfur group, or carbon Hydrocarbon groups having one or more atoms, such as methylene and ethylene.

Is it suitable as a constituent residue of the Group 1 VB transition metal component in this catalyst system? Non-limiting CT group Specific examples include dimethylsilyl, diethylsilyl, di-n-propylsilyl, di- Sopropylsilyl, di-n-butylsilyl, di-t-butylsilyl, di-n- xylsilyl, methylphenylsilyl, ethylmethylsilyl, diphenylsilyl , di(p-t-butylphenethylsilyl), n-hexylmethylsilyl, cyclo Pentamethylenesilyl, cyclotetramethylenesilyl, cyclotrimethylenesilyl dimethylgermanyl, diethylgermanyl, methylene, dimethylmethylene, Diethylmethylene, ethylene, dimethylethylene, diethylethylene, dipropylene ethylene, propylene, dimethylpropylene, diethylpropylene, 1,1- Dimethyl 3-3-dimethylpropylene, tetramethyldisiloxane, 1,1.4 ．． 4-tetramethyldisilylethylene, oxygen and sulfur.

Representative examples of the hydrocarbon group of X are methyl, ethyl, propyl, isopropyl, butyl , amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, Decyl, cetyl, 2-ethylhexyl, phenyl, etc., but methyl is preferred . Typical examples of halogen atoms in X include chlorine, bromine, fluorine and iodine. However, chlorine is preferred. Representative examples of alkoxides and aryloxides of X are Toxide, ethoxide, propoxide, butoxide, phenoxide, and 4-methoxide Substituted phenoxytes such as tylphenoxyto. A typical example of the amide of Methylamide, diethylamide, methylethylamide, di-t-butylamide, diisopropylamide, etc.

Typical examples of arylamides are diphenylamide and other substituted phenylamides. Ru. Typical examples of silylamides are di-trimethylsilylamide and di-triethylsilylamide. Lylamide and triethyl-trimethylsilylamide, but ditrimethylsilylamide Rylamide is preferred. Typical examples of phosphites of X are diphenyl phosphite, di Cyclohexyl phosphite, diethyl phosphite, dimethyl phosphite, etc. . Typical examples of alkylidene groups in which two Xs are combined are methylidene and ethylidene. , propylidene, or ethylene glycol dianion.

Suitable hydrocarbon and substituted hydrocarbon groups for the R group are from 1 to about 30 carbon atoms; - or an alkyl group having multiple branches, a cyclic hydrocarbon group, an alkyl-substituted cyclic carbon Hydrocarbon groups, aromatic groups and alkyl-substituted aromatic groups, amide-substituted hydrocarbon groups, phosphides t-substituted hydrocarbon group, alkoxy-substituted hydrocarbon group, and halo-substituted hydrocarbon group or Included are hydrocarbon groups substituted with Lewis base or Lewis acidic functional groups. R group Suitable organometallic groups include trimethylsilyl, triphenylsilyl, and triphenylsilyl. Contains phenylgermyl, trimethylgermyl, etc. Other suitable R groups Groups include amide groups, phosphite groups, alkoxy groups, alkylpolide groups, etc. It will be done. Among the preferred R groups, trimethylsilyl, triethylsilyl, ethyldimethy Organometallic groups of silicon such as tylsilyl and methyldiethylsilyl are preferred; Most preferred is trimethylsilyl.

By converting all possible combinations of component parts into each other, many final products can be created. minutes arise. An exemplary transition metal compound is bis(di-trimethylsilylamide) Zirconium dichloride, bis(di-isobutyramide) hafnium dimethyl , bis(di-tertbutyramide)zirconium dichloride, (zylcyclo hexylamide) (di-trimethylsilylamide) titanium dihydride, tris( di-trimethylsilylamide) zirconium chloride, tris(di-triphene) hafnium chloride and tetrakis(di-trimethylsilane) lylamido) zirconium.

The group rVB metal compound is made of isotactic polypropylene with high stereoregularity. It has been used in manufacturing. As demonstrated in Example 9, the achiral compound bis Combining (di-trimethylsilylamide) zirconium dichloride with alumoxane When combined to form a catalyst system, this system contains less than 50 chains per 1000 monomer units. It is possible to produce isotactic polypropylene that has only defects. of this type Methods for preparing the compounds are well known from the literature, including R.A.

Anderson, Inorganic Chemistry, 18.29 28 (1979).

B. Alumoxane component The alumoxane component of the catalyst system has the general formula (R3-^1-0), (cyclic compound) or Oligomer represented by R4 (R5-^1-0-), -AIR6□ (linear compound) -It is a compound. Alumoxane is generally a mixture of linear and cyclic compounds . In the above general formula of alumoxane, R3, R4, R5 and R6 are independently C5 alkyl group, specifically methyl, ethyl, propyl, butyl or pentyl and m is an integer from 1 to about 50. Most preferably R3, R4, R5 and Each R6 is methyl, and m is 4 or more. Alkium for the production of alumoxane When using aluminum halide, one or more of the R3-R6 groups is a halide. You can.

As is well known today, alumoxanes can be produced in different ways. can. For example, to obtain alumoxane, trialkylaluminum is wetted with May be reacted with water in an inert organic solvent or trialkylaluminium may be reacted with a hydrated salt (such as a hydrated sulfate suspended in an inert solvent). in general, The reaction of trialkylaluminum with a limited amount of water, no matter how it is produced, gives a mixture of both linear and cyclic species of alumoxane.

Preferred alumoxanes that can be utilized in the catalyst system of the present invention include trimethylalcohol aluminum, triethylaluminum, tripropylaluminum, triisobutylene aluminum, dimethylaluminum chloride, diisobutylaluminum Trialkylaluminium, such as chloride, diethylaluminum chloride, etc. or produced by hydrolysis of haloalkylaluminum. use The most preferred alumoxane available is methylalumoxane (MAO). flat Methylalumoxane having a uniform degree of oligomerization of from about 4 to about 25 (i.e., from 4 to 25) are preferred, and those in the range of 13 to 25 are most preferred.

C1 catalyst system The catalyst system used in the present invention comprises an amide Group I VB transition metal compound and an alumoxane component. It comprises a complex formed by mixing. Required bis-amide Group 1 VB transition metals component and alumoxane component by solution polymerization method, slurry polymerization method, or bulk polymerization method. by adding it to an inert solvent in which the olefin polymerization can be carried out. A catalyst system may also be produced.

The catalyst system comprises a selected amide Group I VB transition metal component and a selected alumoxane component. and, in the desired order, an alkane or aromatic hydrocarbon solvent (preferably a polymerization diluent). It can also be conveniently prepared (preferably used as If the hydrocarbon solvent is also suitable for use as a polymerization diluent, Catalyst systems may also be prepared in situ. Alternatively, the catalyst system can be kept in a concentrated state. It may be prepared separately and added to the polymerization diluent in the reactor. Also, depending on your wishes , each component of the catalyst system is prepared as a separate solution, and suitable (e.g. continuous liquid phase polymerization) The diluent may be added to the diluent in the reactor in proportions (as appropriate for the reaction process). Catalyst system combination Alkanes and aromatic hydrocarbons suitable as polymerization solvents and polymerization diluents. Also includes straight chain substances such as isobutane, butane, pentane, hexane, heptane, octane, etc. or branched hydrocarbons, cyclohexane, cyclohebutane, methylcyclohexane cyclic or alicyclic hydrocarbons such as methylcyclohebutane, benzene, Examples include aromatic and alkyl-substituted aromatic compounds such as toluene and xylene. Yes, but not limited to these. Suitable solvents include ethylene, Produced as a monomer or comonomer, such as propylene, 1-butene, 1-hexene, etc. Mention may also be made of the liquid olefins that can be used.

In the present invention, optimal results are generally obtained when the amide Group IB transition metal compound is polymerized. present in the diluent at a concentration of about 0.0001 to about 1.0 mmol/liter diluent; , and the alumoxane component is about 11 to about 20,000:1 aluminum/transition It is obtained when present in an amount such that the metal molar ratio. suitable from the catalyst components during the reaction. Enough solvent must be used to properly transfer heat and mix well. .

Components of the catalyst system (i.e., amide Group TVB transition metal, alumoxane, and polymerization diluent) ) may be added to the reaction vessel rapidly or gradually. When catalyst components come into contact The temperature maintained can vary widely, for example from -10°C to 300°C. It can be changed with . Higher or lower temperatures may also be used. Wear. Preferably 1. During preparation of the catalyst system, the reaction is maintained at a temperature of about 25°C to 100°C. most preferably at about 25°C.

At any time, the individual catalyst system components, as well as the catalyst system once formed, are exposed to oxygen and water. protect from Therefore, the reaction to produce the catalyst system is carried out in an oxygen-free and anhydrous atmosphere. If the catalyst system is recovered separately, the catalyst is kept in an oxygen-free and moisture-free atmosphere. Collect it below. Therefore, preferably the reaction is carried out using an impurity such as helium or nitrogen. Performed in the presence of active drying gas.

D. Polymerization method In a preferred embodiment of the process of the invention, the catalyst system comprises an olefinic monomer. , liquid phase (slurry, solution, suspension or bulk phase or a combination thereof), high pressure fluid phase or used in gas phase polymerization. These processes may be used singly or sequentially. liquid The phase process involves the steps of contacting the olefin monomer with a catalyst system in a suitable polymerization diluent; and the monomer in the presence of a catalyst system sufficient to produce a high molecular weight polyolefin. the step of reacting at a time and temperature of minutes.

The monomers used in such processes are those used to produce isotactic polypropylene. In the case of using propylene, it consists only of propylene. Production of isotactic polypropylene The most preferred conditions are to introduce propylene into the reaction zone from about 0.019 psi to about 5000 psi The reaction temperature is maintained at about -100°C to about 300°C. Is Umono. The molar ratio of aluminum to transition metal is preferably from about 1:1 to 20000:1. A more preferable range is 1:1 to 2000:1. Ru. The incubation time is preferably about 1 hour to about 6 hours.

In addition, when manufacturing polyethylene homopolymer, only ethylene is used as the monomer. When producing an ethylene/α-olefin copolymer, ethylene and carbon are It consists of an α-olefin having 3 to 20 elementary atoms. High-grade α-oleph such as butene homopolymers of ethylene and/or higher alpha-ols of C4 or higher. Copolymers with olefins and diolefins can also be produced. ethylene monomer The most preferred conditions for homopolymerization or copolymerization are approximately 0.019 ps of ethylene in the reaction zone. i to about 50,000 psi, and the reaction temperature was about -100°C to about 30°C. The temperature is maintained at 0°C. The molar ratio of aluminum to transition metal is favorable. Preferably, the ratio is about 1:1 to 20,000:1. A more preferable range is 1:1 to 2. 000+1. The reaction time is preferably about 10 seconds to about 1 hour.

Although not intended to limit the technical scope of the present invention, regarding the production of copolymers , one means of implementing the method of the invention is as follows. For stirred tank reactor A liquid alpha-olefin monomer such as 1-butene is introduced. Catalyst system in gas phase or It is delivered through a nozzle as a liquid phase. The feed ethylene gas is supplied in a manner well known to those skilled in the art. It is fed into the gas phase of the reactor or dispersed into the liquid phase. The reactor contains dissolved ethylene A liquid phase consisting essentially of gas and liquid alpha-olefin comonomers and all monomers - Contains a gas phase containing steam. The temperature and pressure of the reactor are Controlled by monomer reflux (self-cooling) and cooling coils, cooling jackets, etc. control The rate of polymerization is controlled by the concentration of catalyst. polymer product ethylene The content is determined by the ethylene/α-olefin comonomer ratio in the reactor However, this ratio can be controlled by manipulating the relative feed rates of these components to the reactor. be controlled.

Paddle stirrer, external water jacket for temperature control, dry nitrogen, ethylene, propylene Flow control supply devices for 1-butene, 1-butene and hexane, and other solvents or is a septum for delivering comonomer, transition metal compound and alumoxane solution The polymerization operation was carried out in a 1 liter autoclave reactor equipped with an inlet. for use First, the reactor was completely dried and degassed. A typical operation is a 400m1 5ml of 1.0M MAo, 0.27mg of [(Me3Si)zN]2z Inject rC1z (0.2 ml of 13.5 Mg in 10 ml of toluene solution) into the reactor. It consisted of doing. The reactor was then heated to 80°C and ethylene (60p sf) was introduced into the device. The polymerization reaction was limited to 10 minutes. Cools down equipment quickly The reaction was stopped by evacuation. Evaporate the solvent from the polymer with a stream of nitrogen I left. Polyethylene was recovered (7.4g, 1W=315000゜MfD= 2.261).

Example 2 Using the same reactor design and general procedure as in Example 1, 400 ml of toluene, 5.0 ml of 1.0M MAo and 0.32 mg of [(Me3Si)2N CoJf C1:+ (0.2ml of 1.60mg in 10ml of toluene solution) into the reactor Added. Heat the reactor to 80°C and introduce ethylene (60psi) to start the reaction. After 10 minutes, the apparatus was rapidly cooled and evacuated. After evaporating toluene, 2 ．． 7g of polyethylene was recovered (MW=267200°MWD=2.122) .

Example 3 Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 100ml propylene, 7.0ml 1.0MMAO and 1.35mg [(Me,Si)2N12ZrC12 (13.51 in 10 ml toluene solution) 1 ml) was added to the reactor. Heat the reactor to 50°C and introduce ethylene. After the reaction was run for 30 minutes, the apparatus was rapidly cooled and evacuated. Toluet After evaporation of the ethylene/propylene copolymer, 9.3 g of ethylene/propylene copolymer was recovered (MW =131000. MID・1.837. Short chain branching number (SCB) by IR method )=121.7/100OC).

Example 4 Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 100 ml of propylene, 7.0 ml of 1.0 MMAO and 1.6 mg of [(M e, 5i) 2N] 2BfC1z (16 mg in 10 ml toluene solution 1 ml ) was added to the reactor. Heat the reactor to 80°C and introduce 60p of ethylene. si) After the reaction was carried out for 30 minutes, the apparatus was rapidly cooled and evacuated. Steaming toluene After evaporation, 8.2 g of ethylene/propylene copolymer was recovered (MW=80 700. MWD=1.537. 5CB by IR = 89.3/100OC) .

Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1. OMMAO and 1.35 mg of [ (Me, 5i)2N]2ZrC12 (13.5 mg in 10 ml toluene solution) 1) 1) was added to the reactor. Heat the reactor to 80°C and introduce ethylene. 60 psi) for 30 minutes, then the apparatus was rapidly cooled and evacuated. Toluet After evaporation of the ethylene/butene copolymer, 4.3 g of ethylene/butene copolymer was recovered (MW=9 1100. MWD=1.643. "C-NMRl, :, Yoru SCB・51 ．． 4/100OC).

Example 6 Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1. OMy^0 and 1.6 mg [(M esSi)2N]JfCIz (16mg in 1ml of 10ml toluene solution) was added to the reactor. Heat the reactor to 80°C and feed ethylene at 60 ps. i) After running the reaction for 30 minutes, the apparatus was rapidly cooled and evacuated. evaporate toluene After that, 9.3 g of ethylene/butene copolymer was recovered (MW=70800 ．． MWD=1.710. "C-NMRi, -Yor5CB=46.8/100 OC).

Example 7 Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1. OMMAO and 1.35 mg of [ (Me3Si)2N]2ZrC12 (13.5ωg in 10ml toluene solution) 1 ml) was added to the reactor. Heat the reactor to 80℃ and pump ethylene thickly. 60 psi) for 30 minutes, then the apparatus was rapidly cooled and evacuated. Thor After evaporating the ene, 13.9 g of ethylene/hexene copolymer was recovered (with lid). 'I=111200. l! 1D=1.782. 5CB by IR = 32.2 /100OC).

Example 8 Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1. OMMAO and 1.6 mg [( 11e3.5l) 2N co2tlfc12 (16mg in 10ml toluene solution 1 ml) was added to the reactor. The reactor was heated to 50°C and ethylene was introduced. After 30 minutes of reaction (65 psi), the apparatus was rapidly cooled and evacuated. Tor After evaporating the ene, 8.7 g of ethylene/hexene copolymer was recovered (li l = 2367 (to, 11tD・1.780. 5CB by IR = 20.1 /100OC).

Example 9 Using the same reactor design and general procedure as in Example 1, 100 ml of toluene, 200 ml of propylene, 10.0 ml of 1. OMMAO and 10ml toluene 128.3 mg of [(MesSi)2N]zZrc was added to the reactor. reaction The vessel was heated to 30°C and the reaction was carried out for 3 hours, after which time the apparatus was rapidly cooled and evacuated.

After evaporating the toluene, 3.2 g of isotactic polypropylene was recovered. (Mf=95500.MWD=1.758.”As measured by C-NMR With 40 chain defects per 1000 monomer units, 90% (m) isotactic (melting point: 146°C).

Example 10 Polymerization can be carried out at temperatures up to 300°C and pressures up to 2500 bar. The experiments were carried out in a 100 ml stirred stainless steel autoclave equipped with the following equipment. reactor was degassed, purged with nitrogen, purged with ethylene and heated to 202°C. Komono 1-hexene (75 ml) was added to the reactor under ethylene pressure. [(M e3Si)2N]2Zrc12 in 25 ml of toluene. It was prepared by dissolving 7.6 mg of the compound.

The test solution was prepared by adding 2.5 ml of the above stock solution to 10.0 ml of 1.0M MAO solution. Prepared by adding. Constant volume of the above test solution (0.43ml) under nitrogen pressure. Transferred to injection tube. Autolave was pressurized with ethylene to 1792 bar and 180 bar Stirred at 0 rpm.

The above test solution (0.43 ml) was injected into the autoclave under overpressure; A temperature increase of 10°C was observed. Continuously records temperature and pressure for 120 seconds After 120 seconds, the contents of the autoclave were rapidly evacuated and transferred to a receiver.

The reactor was flushed with xylene to recover any residual polymer. This washing product is It mixed with the polymer released when the reactor was evacuated. From the mixture by adding acetone When the polymer was precipitated, 1.3 g of ethylene/hexene copolymer was obtained. (MW=42000.MID・2.07.SCB・8.9/1 by IR 00OC).

Example 11 Using a reactor of the same design as described in Example 10, the reactor was degassed and flushed with nitrogen. Purged with ethylene, heated to 199°C. Comonomer 1-hex Sen (75 ml) was added to the reactor under ethylene pressure. [(Meqsi) 2N] 2BfCb stock solution is 9.5ml of the transition metal compound in 25ml of toluene. It was prepared by dissolving 0 mg. The test solution was 2.5ml of the above stock solution in 10.0ml 1 of l. Prepared by adding to OMMAQ solution. The above test solution (0, 43 ml) was transferred to a constant volume injection tube under nitrogen pressure. autoclave with ethylene It was pressurized to 31 bar and stirred at 1800 rpm. Automate the above test solution with overpressure A temperature increase of 7° C. was observed during the injection into theclave. Temperature and pressure 1 Continuously record for 20 seconds, and after 120 seconds, the contents of the autoclave are It was quickly evacuated and transferred to a receiver. Clean the reactor with xylene to remove any residual polymer. It was collected. This wash was mixed with the polymer released during reactor venting.

When acetone was added to precipitate the polymer from the mixture, 0.5 g of ethylene was added. A hexene/hexene copolymer was obtained (M?=57000゜MWD=2.22.I 5CB by R=8.0/100OC).

The invention has been described with reference to preferred embodiments. Those skilled in the art will Various changes or modifications may occur to you upon reading the specification, but they do not apply to this specification and This does not deviate from the technical scope and spirit of the invention as set forth in the claims. .

international search report tmm＾-1・I″a@-・l+IM/IIQQ1ノnogtc front page Continued (51) Int, C1,5 identification code Office reference number CO8F 210102 I

Claims (17)

[Claims] 1. A compound represented by the general formula below. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, y is 1 and represents the presence of a bridging group between nitrogen atoms, and z is 2-y, M is zirconium, hafnium or titanium, and N is three positions. is a nitrogen atom having a substituent, and each X is independently a halide, a hydride, a substituted or Unsubstituted C1-C30 hydrocarbons, alkoxides, aryloxides, amides, ants monovalent anionic ligands such as arylamides, phosphides or aryl phosphides and T is an unsubstituted hydrocarbon containing a Group IVA or Group VIA element; a covalent bridging group selected from the group consisting of substituted hydrocarbons, each R independently Hydrocarbons having 4 to 30 carbon atoms with one branch, carbons with multiple branches Hydrocarbon having 4 to 30 atoms, halogen group, amide group, phosphide group, silyl group , an alkoxy group, an alkylboride group, a C1-C30 hydrocarbon substituted Group VA metalloid group, and one or more substituted C1-C30 hydrocarbon groups hydrogen atom is a halogen group, amide group, phosphide group, alkoxy group or other C1-C substituted by a group containing a Lewis acid or Lewis basic functional group 30 hydrocarbon groups. 2. As a catalyst system for α-olefin polymerization, the following composition a) The following general according to claim 1: Compounds with the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the above formula, y is 1 or 0, and each indicates the presence or absence of a bridging group between nitrogen atoms. z is 2-y, M is zirconium, hafnium or titanium , N is a nitrogen atom with three substituents, and each X is independently a halide, a hydrogen atom, Dolide, substituted or unsubstituted C1-C30 hydrocarbon, alkoxide, aryl such as oxides, amides, arylamides, phosphides or arylphosphides. It is a monovalent anionic ligand, and T is a group IVA or group VIA element. a covalent bridging group selected from the group consisting of unsubstituted hydrocarbons and substituted hydrocarbons; and each R independently represents a hydrocarbon having 4 to 30 carbon atoms having one branch; Hydrocarbons having 4 to 30 carbon atoms with several branches, halogen groups, amide groups, Suphide group, silyl group, alkoxy group, alkylboride group, C1-C30 carbonization Group IVA metalloid groups substituted with hydrogen and substituted C1-C30 hydrocarbon groups and one or more hydrogen atoms are halogen group, amide group, phosphide group, substituted by a group containing a Coxy group or other Lewis acid or Lewis basic functional group. is a group selected from the group consisting of a C1-C30 hydrocarbon group, and b) Alumoxane A catalyst system comprising. 3. In the compound according to claim 1 or the system according to claim 2, each R independently represents a halogen. ion group, amide group, phosphide group, silyl group, alkoxy group, alkylboride group , Group IVA metalloid groups substituted with C1-C30 hydrocarbons, and substituted C1- A C30 hydrocarbon group in which one or more hydrogen atoms are a halogen group, an amide group, Phosphide group, alkoxy group or other Lewis acid or Lewis basic functional group selected from the group consisting of C1-C30 hydrocarbon groups substituted by a group containing A compound or system characterized by being a group. 4. The compound or system according to any one of claims 1 to 3, wherein T is Compounds or systems characterized by being covalent bridging groups containing group IVA atoms . 5. A compound or system according to any one of claims 1 to 4, comprising at least A compound or system characterized in that both R's are silicon-containing groups. 6. A compound or system according to any one of claims 1 to 5, comprising at least A compound or system characterized in that both X's are nitrogen-containing groups. 7. In the compound or system according to any one of claims 1 to 6, each X is independently from the group consisting of hydrides, alkoxides, amides, hydrocarbons and halides A compound or system characterized in that it is selected. 8. 8. The compound or system according to claim 7, wherein at least one X is hydride, carbon Compound selected from the group consisting of hydrogen hydride, amide and halide Or system. 9. In the compound or system according to any one of claims 1 to 8, M is A compound or system characterized in that it is ruconium or hafnium. 10. The catalyst system according to any one of claims 2 to 9, wherein the alum xane is trimethylaluminum, triethylaluminum and triisobutyl obtained by hydrolysis of an aluminum alkyl selected from the group consisting of A catalyst system characterized by: 11. The catalyst system according to any one of claims 2 to 15, wherein aluminum A catalyst system characterized in that the ratio of aluminum to transition metal is 1:1 to 20,000:1. 12. A method for producing polyα-olefin, comprising: a) the method according to claims 1 to 11; A catalytically active combination comprising a compound or system according to any one of the claims contacting the α-olefin monomers, and b) A method comprising the step of recovering poly-alpha-olefins. 13. In the method according to claim 12, the polyα-olefin produced is It is tactical polypropylene, and the monomer in a) above is propylene. A method characterized by: 14. In the method according to claim 12, the polyα-olefin produced is a polyester. A copolymer of tyrene or ethylene and an α-olefin having 3 to 20 carbon atoms, The monomer a) is ethylene or ethylene and α-oleph having 3 to 20 carbon atoms. A method characterized in that the method comprises: 15. In the method according to claim 12, claim 13 or claim 14, the polymerization time is 1 to 6 hours and/or the pressure is 0.13 kPa (0.019 psi) to 3 44,75 MPa (50,000 psi) and/or the reaction temperature is -100 A method characterized by maintaining the temperature between °C and 300 °C. 16. 16. The method of claim 15, wherein the polymer produced has a MW of 1.5 to 3. A method characterized by having D. 17. In the method according to claim 15 or 16, the polymer produced is 5 A method characterized in having an SCB of ~150.